Production of pattern effects upon textile fabrics or other materials



.2a effected simultaneously.

Patented Aug. 15, 1933 PRODUCTION OF PATTERN EFFECTS UPON TEXTILE FABRICS RIALS George. Holland Ellis OR OTHER MATE- and William Bertram Miller, Spondon, near Derby, England, assigncrs to Celanese Corporation of America, a Corporation of Delaware No Drawing. Application October 7,

398,089, and

Serial No. November 3, 1928 13 Claims.

"" {This invention relates to a new process for the production of pattern or discharge or resist ef fects upon textile fabrics or other materials, the new process being of particular value in the treatment of fabrics or other materials made of or containing cellulose acetate or other organic esters of cellulose or made of or containing cellulose ethers.

According to application Serial No. 391,692 filed 19 Sept. 10, 1929 corresponding to British applications Nos.'27962/28, 32105/28 and 18962/29 of one of the present inventors, in the production of azo coloring matters on textile fabrics or other materials by diazotizing amines or amino coloring ,15 matters on the material and developing, discharge or fresist effects are produced by treating the materials locally before diazotization and development so as to render the amines or amino coloring matters in selected areas incapable of 29 forming coloring matters by diazotization and development. The developer components may be appliedbefore the diazotization, for example together with the amines or amino coloring mat- "ters gsothat upon diazotization development is The said application instances the use ,of 'chlorates, chromates or other oxidizing discharges for the purpose of rendering the amines or amino coloring matters incapable of forming coloring matters by diazotization and development.

We have now found that sulphoxylates, hydrosulphites or other reducing discharges may likewise be applied to the materials so as to render amines, or amino coloring matters incapable of forming coloring matters by diazotization and development. Such a treatment of amines or amino coloring matters is entirely novel and constitutes a remarkable and valuable advance in the art of discharge printing.

{9 On account of the ease with which amines may be incorporated in cellulose esters and ethers the processes of the invention are of particular value as applied to materials containing such cellulosederivatives. The invention is however applicable to the discharge of amino coloring mat ters and to the production of the pattern eflfects upon materials other than cellulose derivatives.

As examples of amino bases and amino coloring matters on the one hand, and developers or coupling components on the other hand, which may be used for the purpose of the presentinvention, the following may be instanced, though the listing of these examples implies no. limitation of the invention thereto.

1929, in Great Britain Amino bases and amino coloring matters Deoelopers or coupling components Xylidines, cresidines, anisidines, phenetidines, metatoluidine, metaphenylenediamine, nitrometaphenylenediamine, alkyl-, arylor aralkylanilines, phenols, cresols, resorcinol, amino-phenols or alkylamino-phenols, such as dimethylmeta'amino-phenol, 11- or ,B-naphthylamines or alkyl derivatives thereof, or naphthylamine ethers, w-oxy-ethyl-a-naphthylamine, -chlor-poxy-propyl- -naphthylamine, (condensation of oznaphthylamine and epichlorhydrin) aminonaphthoic acids, aminomaphthols, or any compounds obtained by the acetylation or other acidylation of aminogroups in the said coupling components.

The aminoazo coloringmatters to be used for discharge purposes according to the present invention may of course be applied as such or they may be produced on the material itself before the application of the discharge. Furthermore in the case of aminoazo bodies, the invention contemplates a partial reduction to amino bases. ,so that, upon diazotization and if necessary development, one color is produced upon the undischarged portions due to the coupling of the diazotized aminoazo compound with the developer and another. color is produced upon the dis-- charged portions due to the coupling of the diazotized amino bases (obtained from the aminoazo bodies) with the developer.

As reduction discharges for thepurpose of the present invention we prefer to employ formaldehyde sulphoxylates or similar reduction discharge agents, the action of which is developed only upon steaming. Other reduction discharges may however be employed, for example sodium hydrcsulphite, stannous chloride and the like. The concentration of the discharges and the conditions under which they are applied will be adjusted in accordance with the requirements of the particular amino base or amino coloring matter to be discharged. In general more vigorous conditions are required than those necessary to produce the ordinary reduction discharges known in the art.

To obtain colored discharges, coloring matters, which resist the action of the discharges sufficiently and also the diazotizing and development processes, may be incorporated in the discharge pastes or like compositions. Vat colors of theanthraquinone and indigoid series are particularly useful, and may be employed either in their usual form or in the form of the esters of their, leuco compounds, such as Indigosols and Soledon colors, the nitrous acid of the diazotizing bath serving to effect the oxidation and fixation of the leuco compound.

As indicated above the developer may be applied to the fibre together with the amino base or the like before the local application of the discharging agent, the final development being by means of nitrous acid. The materials before treatment with nitrous acid are preferably dried and aged or steamed.

The discharge effects may be obtained with any suitable means of local application, for example machine or hand-block printing, spraying, stencilling or the like.

As indicated above the most valuable results may be obtained according to the present invention on materials containing organic esters of cellulose, for example cellulose acetate, cellulose formate, propionate or butyrate, or the products obtained by the treatment of alkalized cellulose with esterifying agents (e. g. the product known as immunized cotton obtained with paratoluene sulpho-chloride) or containing cellulose ethers, for instance methyl, ethyl or benzyl cellulose or the corresponding condensation products of cellulose and glycols or other polyhydric alcohols. However, in addition to obtaining pattern effects on materials comprising cellulose esters and/ or ethers, the processes of the present invention may be used to obtain effects on materials made of or containing other fibres, for instance cotton or the cellulosic type of artificial silk.

Effects may moreover be produced on mixed goods containing, for example, cellulose acetate or other cellulose esters and/or ethers in association with other fibres, for instance cotton or the cellulosic type of artificial silk. Furthermore, such mixed goods may be dyed differentially by utilizing the property of the cellulose ester portion of absorbing amines substantively from solution, in preference to their absorption by the other components. Differential or uniform shades may be obtained by means of colors hav ing an affinity for the non-ester portion but which resist cellulose esters. According to the effect desired, such coloring matter for the non-ester portion of the mixed goods may be so chosen that they are either discharged by or resist the discharging agents employed; further they may if desired be selected so that they either resist or respond to the diazotization and development operations.

The following examples are intended to illustrate the invention but not to limit it in any way:-

Example 1 A woven fabric composed of cellulose acetate yarns is dyed with 1% of its weight of aminoazotoluene in a dyebath whose volume ratio is :1, the aminoazotoluene having been previously dispersed by heating with sodium sulphoricinoleate. The dyeing is allowed to proceed for 1 /2 hours at 80 C. when the fabric is washed and dried at a low temperature, and further prepared for printing as desired. It is now printed by roller printing machine with the following printing paste:-

648 grams gum arabic 1:1

grams zinc oxide '72 grams anthraquinone 10% paste 60 grams glycerine 120 grams water 240 grams sodium formaldehyde sulphoxylate After printing the material is fried and steamed in the cottage steamer for 5 minutes with steam at 5 lbs. pressure or given an equivalent steaming in the rapid ager at 100 C. after which it is diazotized for half an hour in a cold bath containing 5% of its weight of sodium nitrite and 16% of its weight of hydrochloric acid 28 Tw. When diazotization is complete the fabric is washed well in cold water and developed in known manner with 2% of its weight of fi-oxy-naphthoic acid. It is then rinsed, soaped lightly and otherwise treated and finished as desired or requisite. The unprinted parts are a bluish red, the printed parts being discharged white.

Example 2 A woven fabric composed of cellulose acetate yarns is dyed in the same manner as in'Example 6 with 2% of its weight of dimethylaminobenzeneazoalphanaphthylamine. It is then printed with a paste composed as follows:

540 grams gum arabic 1:1

50 grams zinc oxide I 60 grams anthraquinone 10% paste 50 grams glycerine 100 grams water 200 grams Formosul After drying the material is steamed in the- Example 3 A fabric composed of cellulose acetate yarns is treated in a 50 :1 bath with 1% of its weight of dianisidine previously dispersed by heating with sodium sulphoricinoleate. The dyeing is continued for 1 /2 hours at C. after which the fabric is washed and dried at a low temperature and further prepared for printing as desired.

roller printing machine with a It is then printed by roller printing machine with a paste composed as follows:

550 grams gum arabic 1:1

30 "grams Durindone red Y, Color Index No.

1226 grams caustic soda. 100 grams methylated spirit grams soda ash grams anthraquinone 10% paste 30 grams sodium hydrosulphite 200 grams Formosul rout After drying, the printed material is steamed in the cottage steamer for 15 minutes at 5 lbs. pressure, after which it is entered into a cold 50:1 bath containing 5% sodium nitrite and 16% hydrochloric acid 28 Tw. calculated on the weight oi -material. After diazotizi-ng for 4 hour during which the leuco compound of the vat dyestufi oxidized and fixed on the fibre, the fibre is well washed in cold water and developed in known manner with 3% of its weight of e-oxynaphthoic mid. It is finally rinsed, soaped lightly and otherwise treated and finished as desired or requisite. The printed portion is red, on a'navy blue gr Example 4 A woven fabric composed of cellulose acetate warp and viscose weft is dyed with 1% of its weig-htof aminoazotoluene and 1% of Diazamine Bordeaux B (Sandox), the aminoazotoluene bedug dispersed by heating with sodium sulphoricinoleate before adding to the neutral dyebath containing the soluble color for the viscose. After dyeing has proceeded for 1%; hours at 80 Qmater ial is washed well, dried and prepared for printing as desired. It is now printed by printing paste composed as follows:

648 grams agum arabic 1:1

grams zinc oxide 'lzmsbinthraquinone 10% paste 60 grams glycerine 120 grams water 240 grams Formosul After printing, the material is dried and steamed in the cottage steamer for 5 minutes with steam at 5 lbs. pressure or given an equivalent steaming in the rapid ager at 100 C, after which it is diazotized for half an hour in a cold bath containing 5% of its weight of sodium nitrite and 16% of hydrochloric acid 28 Tw. When diazotization is complete the fabric is washed well in cold water and developed in known manner with 2% of its weight of betaoxynaphthoic acid. It is then rinsed, soaped lightly and otherwise treated and finished as desired or requisite. The unprinted portions are a bluish red, the printed parts white.

Example 5 Fabric composed of cellulose acetate yarns is dyed in a mixture of 0.5% of o methoxybenzeneazoalphanaphthylamine and 1% of B-hydroxy naphthoic acid paranitroanilide, calculated on the weight of material. (The Naphthol A838 is dissolved in aqueous caustic soda and poured into the dyebath prepared with 2 cos. of sodium sulphoricinoleate per litre. The bath is now just neutralized with dilute acetic acid and the solution of the above amine, previously dispersed by heating with aqueous sodium sulphoricinoleate, added). Dyeing is continued for 1 hours at C.and the material well washed, dried and otherwise prepared for printing as desired. It

is then printed with a paste composed as follows:-

The printed and dried material is given a passage through the rapid ager at C. or a short steaming in the cottage steamer at 5 lbs. pressure, after which it is developed for 1% hours in a cold bath containing 4 grams per litre of sodium nitrite and 8 grams per litreof acetic acid. The fabric is finally rinsed and soaped and otherwise treated as desired or requisite. A red pattern on a navy ground results.

Example 6 Fabric composed of cotton or other cellulosic yarn is dyed by known methods with 5% of its weight of Chlorazol black BH (Color Index No. 401), washed, dried and prepared for printing. It is then printed on the roller printing machine with a paste composed as follows:

650 grams gum arabic 1:1 200 grams water I 50 grams anthraquinone 1 0% paste 100 grams sodium formaldehyde sulphoxylate The printed fabric is dried and aged in the MatherPlatt rapid ager at 100 C. for 5 minutes Nor given other suitable steaming, after which it is diazotized without any previous washing in a cold bath containing 2 /2% of sodium nitrate and '7 of hydrochloric acid 28 Tw. calculated on the weight of material. After diazotizing for 20 minutes the fabric is washed well in cold water and developed for 20 minutes in a bath containing 3% of metaphenylenediamine dissolved in water with the aid of a little sodium carbonate. The material is finally Washed and soaped. A white pattern on a black ground is obtained.

What we claim and desire to secure by Letters Patent is:-

1. In a process for forming azo coloring matters on textile materials by diazotizing on the materials compounds containing a diazotizable aminogrouping and developing, the production of discharge resist effects by rendering the amino body, before diazotization and development, incapable'oi diazotization in selected areas with the aid of a reduction discharge.

2. In a process for forming azo coloring matters on textile materials comprising an organic derivative of cellulose by diazotizing on the materials compounds containing a diazotizable amino grouping and developing, the production of discharge resist effects by rendering the amino body, before diazotization and development, incapable of diazotization in selected areas with the aid of a reduction discharge.

3. In a process for forming azo coloring matters on textile materials comprising cellulose acetate by diazotizing on the materials compounds containing a diazotizable amino grouping and developing, the production of discharge resist effects by rendering the amino body, before diazotization and development, incapable of diazotization in selected areas with the aid of a reduction discharge.

4. Process for the production of discharge efiects on materials, comprising applying a diazotizable amino compound to the material, applying to the material locally a reduction discharge and treating the amino compound so that it is rendered incapable of diazotization in selected areas, and finally diazotizing and developing.

5. Process for the production of discharge effects on materials containing an organic derivative of cellulose, comprising applying a diazotizable amino compound to the material, applying to the material locally a reduction discharge and treating the amino compound so that it is rendered incapable of diazotization in selected areas, and finally diazotizing and developing.

6. Process for the production of discharge effects onmaterials containing cellulose acetate, comprising applying a diazotizable amino compound to the material, applying to the material locally a reduction discharge and treating the amino compound so that it is rendered incapable of diazotization in selected areas, and finally diazotizing and developing. 1 V I 7. Process for the production of discharge effects on materials containing an organic derivative of cellulose, comprising applying a diazotizable amino compound to the material, applying locally a sulphoxylate discharge and treating the amino compound so that it is rendered incapable of diazotization in the selected areas, and finally diazotizing and developing.

8. Process for the production of discharge effects on materials containing cellulose acetate, comprising applying a diazotizable amino compound to the material, applying locally a sulphoxylate discharge and treating the amino compound so that it is rendered incapable of diazotization in selected areas, and finally diazotizing and developing. a

9. Process for the production of discharge effects on materials containing anorganic derival;

incapable of diazotization in selected areas, and

finally diazotizing and developing.

' 10. Process for the production of discharge effects on materials containing cellulose acetate, comprising applying a diazotizable amino coinpound to the material, applying to the material locally a reduction discharge, drying and ageing to render the amino compound incapable of diazotization in selected areas, and finally diazotizing and developing. 1 11. Process for the production of discharge effects on materials, comprising applying to the material a diazotizable amino compound together with a developer component; applying to the material locally a reduction discharge and treating the amino compound so that it is rendered incapable of diazotization in selected areas, arid finally cliazotizing. 12. Process for the production of dis'cha'rgeeffects on materials containing an organic derivative of cellulose, comprising'applying to the material a diazotizable amino compound together with a developer component, applying to the material locally a reduction discharge and treating the amino compound so that it is rendered incapable of diazotization in selected areas, and finally diazotizing. 3

13. Process for the production of discharge effects on materials containing cellulose acetate,

comprising applying to the material a diazotizable amino compound together with a developer component, applying to the material locally a reduction discharge and treating the amino compound so that it is rendered incapable of diazotization in selected areas, and finally diazotizing.

GEORGE HOLLAND ELLIS.

WILLIAM BERTRAM MILLER.

CERTIFICATE or ooRREmioN.

Patent No. 3,922,728. August 15, 1933.

GEORGE HOLLAND Ems, ET AL.

it is hereby seriified that error appears ii: the printed specification of the above numbered patom. requiring correotion as follows: Page 2, line 126, page 3, lines i1 and 48, for "Formosui" read sodium formaldehyde sulphoxyiate; page 3, line 34, for "(Sandox) read (Sandoz) Color Index No. 32421; and line 71, for "Naphthoi AS.BS" read B-hyroxy naphthoio acid paranitroarziiizi-e; and that the said Leirers Patent shouizi be read with these corrections therein that the same may conform to the record of the case in the Patent ()ffico.

Signed and sealed this i4th day of November, A. 3). 1933.

F. M. Hopkins (Seai) Acting Commissioner of Patents. 

